Biomass master batch

Abstract

To provide a technique that can increase a blending ratio of a biomass material in a biomass master batch containing polypropylene.SOLUTION: An aspect of the present invention is a biomass master batch prepared by kneading rice and polypropylene, wherein an MFR (230°C / 2.16 kgf) of the polypropylene is 10 g / 10 min or more, a melting point is 150°C or less, a flexural modulus is 1,000 MPa or less, and an elongation ratio of the rice is 95% or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a biomass masterbatch. [Background technology]

[0002] Compositions or molded products (e.g. plastic trays, cutlery, etc.) produced by processing biomass (organic resources derived from plants and animals, excluding crude oil, petroleum gas, combustible natural gas, and coal) using chemical or biological methods, in which the biomass material content is 25% or more by weight, are carbon-neutral and can help combat global warming.

[0003] To prepare a composition of biomass material with such a blend ratio, the biomass material can be mixed with a resin to obtain a predetermined blend ratio, and the composition can be prepared in one go, or a composition with a high blend ratio of biomass material (biomass master batch) can be prepared once, and then mixed with a dilution resin to adjust the blend ratio of the biomass material to prepare the composition. The latter form is preferable in that it is possible to easily design the physical properties of the final composition and make it easier to mold, for example, by appropriately selecting the physical properties of the dilution resin.

[0004] In the latter case, in order to make the biomass material content 25% by weight or more (particularly 50% by weight or more), it is necessary to considerably increase the content of the biomass material in the biomass master batch. When mixing rice and polypropylene as the biomass material to produce a biomass master batch with such a high content of biomass material, the high content of the biomass material can cause a bottleneck in that the melt viscosity becomes high, or the equipment can become overtorque or the processing capacity can decrease due to insufficient thermal fluidity, resulting in poor uniform dispersion or aggregation of the biomass material in the composition.

[0005] Therefore, the blending ratio of the biomass material in the composition must be low in reality. For example, the blending ratio of polished rice in the polyolefin resin composition in the example of Patent Document 1 is about 49% by weight. In addition, as specified in claim 1 after amendment in Patent Document 2 as "a concentrate of biomass resin mainly composed of a first resin and a biomass-derived component, the first resin being mainly composed of an olefin-based resin synthesized by a single-site catalyst, the blending amount of the first resin being 5 to 100 parts by weight per 100 parts by weight of the biomass-derived component, and the concentrate of the biomass resin being a raw material of a composite material produced by blending and kneading a second resin to dilute the concentration of the biomass-derived component," even a concentrate (i.e., a biomass master batch) has a blending ratio of the biomass material of less than 50% by weight. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2005-255743 A [Patent Document 2] JP 2009-057531 A Summary of the Invention [Problem to be solved by the invention]

[0007] Resin compositions containing biomass materials at a blending rate of 25% by weight or more (particularly 50% by weight or more) are not only effective in combating global warming, but are also useful for producing injection-molded products, for example. However, as described above, there are technical difficulties in achieving this by mixing the resin with a diluent resin. It is difficult.

[0008] It is not realistic to lower the blending ratio of the diluent resin and increase the blending ratio of the biomass material, since this makes it difficult to design the physical properties, moldability, etc. of the final composition.

[0009] Therefore, an object of the present invention is to provide a technique capable of increasing the blending ratio of a biomass material in a biomass masterbatch containing polypropylene. [Means for solving the problem]

[0010] One aspect of the present invention is a biomass masterbatch produced by kneading rice and polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more. Effect of the Invention

[0011] According to the present invention, a technique can be provided that can increase the blending ratio of a biomass material in a biomass masterbatch containing polypropylene. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a perspective view showing a biomass masterbatch production apparatus according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a front view of FIG. [Diagram 3] FIG. 2 is a plan view of FIG. [Figure 4] FIG. 2 is a diagram showing a first storage space of a first storage unit constituting the biomass masterbatch production apparatus. [Diagram 5] 2 is a diagram showing a plurality of rotating members arranged in a first storage space of a first storage unit constituting the biomass masterbatch production apparatus of FIG. 1. FIG. [Figure 6] 1 is a flowchart illustrating a method for producing a biomass masterbatch according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. In this specification, "X to Y" means "X or more and Y or less", with the numerical values ​​(X and Y) described before and after it being included as the lower and upper limits. When multiple "X to Y" are described, for example, when "X1 to Y1 or X2 to Y2" is described, the disclosure of each numerical value as the upper limit, the disclosure of each numerical value as the lower limit, and the combination of the upper and lower limits are all disclosed (i.e., they are the legitimate basis for amendment). Specifically, amendments to X1 or more, amendments to Y2 or less, amendments to X1 or less, amendments to Y2 or more, amendments to X1 to X2, amendments to X1 to Y2, etc. must all be deemed legitimate.

[0014] <Biomass masterbatch> One aspect of the present invention is a biomass masterbatch produced by kneading rice with polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more. This aspect provides a technology that can increase the blending ratio of biomass material in a biomass masterbatch that contains polypropylene. In this way, by combining a specific rice with a specific polypropylene to produce a biomass masterbatch, the concentration of rice in the biomass masterbatch can be increased. One aspect of the present invention In an embodiment, the rice content is greater than 50% by weight.

[0015] One aspect of the present invention is a biomass masterbatch containing rice and polypropylene, the polypropylene having an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, a rice content of more than 50% by weight, and when 3 g of the biomass masterbatch is flattened using a hot press molding machine (170°C, 15 MPa pressure) together with a 0.3 mm thick stainless steel thickness gauge to prepare a sample, the number of agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less. This aspect provides a technology that can increase the blending ratio of a biomass material in a biomass masterbatch containing polypropylene. Thus, according to the present invention, even if the rice content is high, exceeding 50% by weight, a biomass masterbatch with few agglomerates can be obtained. According to one embodiment of the present invention, the number of aggregated particles is 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0. The aggregated particles are derived from rice and are granular regions that exist in the matrix resin (polypropylene) in a form in which the interface can be identified, and are formed by rice that is not compatible with the resin and remains in the form of fine particles, or by rice that precipitates after compatibility. The aggregated particles can also be expressed as aggregates or aggregates.

[0016] (MFR of biomass masterbatch (190℃ / 10kgf)) In one embodiment of the present invention, the melt flow rate (MFR) of the biomass masterbatch at 190° C. / 10 kgf is more than 1 g / 10 min, 2 g / 10 min or more, 3 g / 10 min or more, 4 g / 10 min or more, 5 g / 10 min or more, 6 g / 10 min or more. In one embodiment of the present invention, the MFR of the biomass master batch at 190° C. / 10 kgf is preferably as high as possible, but if the value is too high, the components may become non-uniform, so that a realistic upper limit may be set to 50 g / 10 min or less, and may be 40 g / 10 min or less, 30 g / 10 min or less, 20 g / 10 min or less, or 10 g / 10 min or less.

[0017] In one embodiment of the present invention, the tensile strength (strength stress) of the biomass masterbatch is 27 MPa or more, 27.5 MPa or more, 28 MPa or more, 28.5 MPa or more, 29 MPa or more, or 30 MPa or more. In one embodiment of the present invention, the tensile strength (strength stress) of the biomass masterbatch is 50 MPa or less, or 40 MPa or less.

[0018] In one embodiment of the present invention, the tensile strength (elastic modulus) of the biomass masterbatch is 1650 MPa or more, or 1700 MPa or more. In one embodiment of the present invention, the tensile strength (elastic modulus) of the biomass masterbatch is 2000 MPa or less, or 1800 MPa or less.

[0019] In one embodiment of the present invention, the tensile strength (elongation) of the biomass masterbatch is 6% or more, 6.5% or more, 7% or more, or 7.5% or more. In one embodiment of the present invention, the tensile strength (elongation) of the biomass masterbatch is practically 20% or less, for example, 10% or less, or 8% or less.

[0020] In one embodiment of the present invention, the biomass masterbatch has a Charpy impact strength of 2.5 kJ / m 2 or more than 2.6 kJ / m 2 That's all.

[0021] In one embodiment of the present invention, the Charpy impact strength of the biomass masterbatch is In reality, 5J / m2 Less than or equal to 3 J / m 2 Less than or equal to 2.8 J / m 2 It may be the following.

[0022] (rice) The biomass masterbatch of one embodiment of the present invention contains rice.

[0023] In one embodiment of the present invention, the elongation rate of the rice used as the raw material for the production of the biomass master batch is 95% or more. If the elongation rate of the raw rice is less than 95%, it is not sufficiently compatible with polypropylene and the desired effect of the present invention cannot be obtained. Here, the elongation rate is measured by the method described in the Examples section. The value of the elongation rate is higher for varieties of rice that cook plumper. For example, rice such as Yumepirika (registered trademark, variety registration number: 20613) has an elongation rate of 95% or more. On the other hand, rice such as Hisui rice (available from Niigata Kenbei Co., Ltd.), Yukinkomai (variety registration number: 16012), and ABC polished rice (available from Niigata Kenbei Co., Ltd.) does not reach an elongation rate of 95%. The predetermined elongation rate may be achieved by using a single variety or by appropriately blending single varieties. Thus, according to one embodiment of the present invention, the rice is a single variety or a blend of single varieties.

[0024] In one embodiment of the present invention, the elongation rate of the rice used in the production of the biomass masterbatch is 97% or more, 99% or more, 101% or more, 103% or more, 105% or more, 107% or more, 109% or more, 111% or more, 113% or more, 115% or more, 117% or more, 119% or more, 121% or more, or 123% or more. In one embodiment of the present invention, the elongation rate of the rice used in the production of the biomass masterbatch is 200% or less, 150% or less, 145% or less, 140% or less, 135% or less, or 130% or less.

[0025] In one embodiment of the present invention, the content ratio of rice in the biomass master batch is 10% by weight or more, 20% by weight or more, 30% by weight or more, 40% by weight or more, more than 50% by weight, 55% by weight or more, 60% by weight or more, 61% by weight or more, 62% by weight or more, 63% by weight or more, 64% by weight or more, 65% by weight or more, 66% by weight or more, 67% by weight or more, 68% by weight or more, or 69% by weight or more. According to the present invention, the combination of the type of rice and the type of polypropylene is appropriate. Therefore, rice and polypropylene are uniformly compatible with each other, and the content ratio of rice in the biomass master batch can be increased. Therefore, the mixing ratio of the dilution resin, which is an important factor for facilitating the design of the physical properties and moldability of the final composition, can be increased. Therefore, the design of the physical properties and moldability of the final composition is facilitated. In this specification, when the content, content ratio, etc. of rice contained in various mixtures such as at least the biomass master batch are mentioned, the content, content ratio, etc. are based on the solid content converted from the moisture content. In this specification, the moisture content is calculated according to the Karl Fischer coulometric titration method (JIS K0113:2005). For example, if the moisture content of rice is 11% by weight and the weight of the rice including water is 78.7 parts by weight, the weight of the rice is 70 parts by weight.

[0026] In one embodiment of the present invention, the rice content in the biomass masterbatch is 90% by weight or less, 89.8% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, or 73% by weight or less.

[0027] The type of rice used as the raw material is preferably polished rice (raw rice) or something derived from it. In addition, something derived from it is polished rice (raw rice) that has been subjected to some kind of processing.

[0028] The structure of the raw rice may be a β structure (crystalline structure). Polished rice (raw rice) can be prepared by removing rice bran from brown rice (rice polishing process). Polished rice (raw rice) may be in the form of ginjo rice (for example, 3-minute to 7-minute polished rice, 4-minute to 6-minute polished rice, etc.). The rice is preferably polished rice, since the size is similar to that of typical resin pellets that are the raw material for the biomass master batch and handling is easy.

[0029] According to one embodiment of the present invention, the average diameter of the raw rice may be 100 μm or more, 110 μm or more, 500 μm or more, 750 μm or more, 1 mm or more, 2 mm or more, 3 mm or more, or 3.5 mm or more (here, the diameter is the maximum diameter when any two points are taken, the same in this specification). According to one embodiment of the present invention, the average diameter of the raw rice may be 15 mm or less, 10 mm or less, 9 mm or less, 8 mm or less, 7 mm or less, 6 mm or less, 5 mm or less, 4.5 mm or less, or 3.5 mm or less. Specifically, a statistically reliable number (or 10, 50, 100, 500, 1000 or more) is arbitrarily selected from a plurality of rice grains, and the arithmetic mean of these is taken. Examples of instruments used for measurement include a caliper (JIS B 7507:2016) and a microscope.

[0030] Rice flour can also be used as the raw rice. As the raw material for rice flour, as mentioned above, polished rice, ginjo rice (3-minute to 7-minute polished rice, 4-minute to 6-minute polished rice, etc.) that has a β structure (crystal structure) is suitable. The average diameter of rice flour can be less than 100 μm or less than 80 μm. The average diameter of rice flour can be 30 μm or more, 40 μm or more, 50 μm or more, or 60 μm or more. An example of an instrument used to measure the average diameter is a microscope, and a statistically reliable number (or 10, 50, 100, 500, 1000 or more) is arbitrarily selected from multiple rice grains, and the arithmetic mean is calculated.

[0031] In one embodiment of the present invention, the biomass master batch may contain a biomass material other than rice. Examples of the biomass material include starch-based materials and woody and herbaceous materials. Examples of the starch-based materials include potato, taro, corn, wheat, rye, beans, and sweet potato. Examples of the woody and herbaceous materials include napier grass, beige grass, bamboo grass, bamboo, cotton, spruce, birch, rice straw, etc.; agricultural waste including bagasse and rice husks; industrial waste including sawmill residues, forest residues, thinning materials, waste building materials, wood chips, etc.; and household waste including waste paper. According to one embodiment of the present invention, of the biomass materials contained in the biomass master batch, 90% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, 99% by weight or more, and 99.5% by weight or more (upper limit: 100% by weight) is rice.

[0032] (resin) The biomass masterbatch of one aspect of the present invention comprises polypropylene. According to one embodiment of the present invention, the polypropylene is unmodified.

[0033] In one aspect of the present invention, the melt flow rate (MFR(230°C / 2.16kgf)) of the polypropylene is 10g / 10min or more. If the melt flow rate (MFR(230°C / 2.16kgf)) of the polypropylene is less than 10g / 10min, the intended effect of the present invention cannot be obtained. In one embodiment of the present invention, the melt flow rate (MFR(230°C / 2.16kgf)) of the polypropylene is 12g / 10min or more, 14g / 10min or more, 16g / 10min or more, 18g / 10min or more, 20g / 10min or more, 22g / 10min or more, or 24g / 10min or more. In one embodiment of the present invention, the melt flow rate (MFR (230° C. / 2.16 kgf)) of the polypropylene is 100 g / 10 min or less, 70 g / 10 min or less, 50 g / 10 min or less, 40 g / 10 min or less, or 30 g / 10 min or less.

[0034] In one embodiment of the present invention, the melting point of the polypropylene is 150° C. or less. If the melting point of the polypropylene exceeds 150° C., the intended effect of the present invention cannot be obtained. In one embodiment of the present invention, the melting point of the polypropylene is 145° C. or less, 140° C. or less, 135° C. or less, or is 130° C. or less. In one embodiment of the invention, the melting point of the polypropylene is 50° C. or more, 60° C. or more, 70° C. or more, 80° C. or more, 90° C. or more, 100° C. or more, 110° C. or more, or 120° C. or more.

[0035] In one embodiment of the present invention, the flexural modulus of the polypropylene is 1000 MPa or less. If the flexural modulus of the polypropylene exceeds 1000 MPa, the intended effect of the present invention cannot be obtained. In one embodiment of the present invention, the flexural modulus of the polypropylene is 950 MPa or less, 930 MPa or less, 910 MPa or less, 890 MPa or less, 870 MPa or less, 850 MPa or less, 830 MPa or less, or 810 MPa or less. In one embodiment of the present invention, the flexural modulus of the polypropylene is 600 MPa or more, 650 MPa or more, 700 MPa or more, 720 MPa or more, or 750 MPa or more.

[0036] In one embodiment of the present invention, the polypropylene content in the biomass masterbatch is 10% by weight or more, 12% by weight or more, 14% by weight or more, 16% by weight or more, 18% by weight or more, 20% by weight or more, 22% by weight or more, 24% by weight or more, or 25% by weight or more. In one embodiment of the present invention, the polypropylene content in the biomass masterbatch is 49.8% by weight or less, 40% by weight or less, 35% by weight or less, 32% by weight or less, 30% by weight or less, 28% by weight or less, or 27% by weight or less.

[0037] In one embodiment of the present invention, the biomass masterbatch may contain a matrix resin other than polypropylene. In this embodiment, the matrix resin other than polypropylene is preferably a polyolefin such as low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), or polybutene, or an ethylene-based copolymer such as ethylene-vinyl acetate copolymer (EVA) or ethylene-ethyl acrylate copolymer (EEA).

[0038] In one embodiment of the present invention, the matrix resin constituting the biomass masterbatch contains polypropylene at 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, 99% by weight or more, or 99.5% by weight or more (the upper limit is 100% by weight).

[0039] In one embodiment of the present invention, the polypropylene is a metallocene polypropylene. The metallocene polypropylene is a polypropylene polymerized by a metallocene catalyst. Examples of the metallocene catalyst include a catalyst containing a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and an organometallic compound or a carrier that is used as needed. Although Ziegler-Natta polypropylene and postmetallocene polypropylene are also known as polypropylenes, there is a risk that the desired effect of the present invention will not be obtained with polypropylenes obtained using catalysts other than such metallocene polypropylenes.

[0040] Commercially available polypropylene may be used. WMX03, WSX03, WSX03A, etc. of the Wintech (registered trademark) series are suitable.

[0041] (Additives) According to one embodiment of the present invention, the biomass masterbatch comprises at least one additive selected from the group consisting of glycerol, polyglycerol, glycerol fatty acid esters, polyglycerol fatty acid esters, (poly)alkylene glycols, and polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof.

[0042] According to one embodiment of the present invention, the glycerin fatty acid ester includes three types of monoester, diester, and triester. More specifically, for example, acetylated glycerides (diacetyl fatty acid monoglycerides) such as acetate monoglyceride, lactate monoglyceride, citrate monoglyceride, diacetyltartaric acid monoglyceride, and glycerin diacetomonolaurate, succinate monoglyceride, polyglycerin condensed linocylic acid ester, and glycerin diacetomonolaurate are included. According to one embodiment of the present invention, the diacetyl fatty acid monoglyceride has an alkyl group having 8 to 15, 9 to 14, or 10 to 13 carbon atoms. According to one embodiment of the present invention, the polyglycerin fatty acid ester has the following structure, where n is, for example, 2 to 6 or 2 to 5, and R is an alkyl group having 11 to 20, 13 to 19, or 15 to 18 carbon atoms.

[0043] [ka]

[0044] According to one embodiment of the present invention, examples of the unsaturated carboxylic acid include maleic acid, maleic anhydride, nadic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, sorbic acid, acrylic acid, etc. Examples of the derivatives of the unsaturated carboxylic acid that can be used include metal salts, amides, imides, esters, etc. of the unsaturated carboxylic acid.

[0045] According to one embodiment of the present invention, the (poly)alkylene glycol is H(OA) n OH Here, A is an alkylene group and n is 1 to 5. According to one embodiment of the present invention, the alkylene group may have 1 to 5, 1 to 4, 1 to 3, or 1 or 2 carbon atoms.

[0046] According to one embodiment of the present invention, the polyolefin resin modified with an unsaturated carboxylic acid or its derivative includes polyethylene or polypropylene modified with an unsaturated carboxylic acid or its derivative. This is obtained by heating and mixing a polyolefin, an unsaturated carboxylic acid or its derivative, and a radical generator in the presence or absence of a solvent. In one embodiment of the present invention, the amount of unsaturated carboxylic acid or its derivative added (modification amount) to the polyolefin resin is 0.1 to 15% by weight, or 1 to 10% by weight. As the additive, a polyolefin resin modified with an unsaturated carboxylic acid or its derivative is suitable. By combining such an additive with a specific rice and a specific polypropylene, the desired effect of the present invention can be obtained. In one embodiment of the present invention, the acid value (mgKOH / g) can also be used as an index of the amount of unsaturated carboxylic acid or its derivative added (modification amount) to the polyolefin resin. The preferred acid value is 20 to 50 mgKOH / g, 30 to 48 mgKOH / g, or 42 to 47 mgKOH / g. The acid value (mgKOH / g) is the value obtained in accordance with JIS K2501:2003.

[0047] In one embodiment of the present invention, the additives may be used alone or in combination of two or more kinds.

[0048] In one embodiment of the present invention, the additive may be solid (pellet-shaped). The average diameter of the additive is preferably 3 to 4 mm. The method for measuring the average diameter of the additive may be the same as the method for measuring the average diameter of rice.

[0049] In one embodiment of the present invention, the content ratio of the additive (the total when two or more kinds are used in combination) in the biomass master batch is 0.2% by weight or more, 0.5% by weight or more, 1.0% by weight or more, 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3.0% by weight or more, 3.5% by weight or more, or 3.7% by weight or more (in terms of active ingredient when the additive is liquid). In one embodiment of the present invention, the content ratio of the additive (the total when two or more kinds are used in combination) in the biomass master batch is less than 40% by weight, 35% by weight or less, 30% by weight or less, 20% by weight or less, 18% by weight or less, 16% by weight or less, 14% by weight or less, 12% by weight or less, 10% by weight or less, 8.0% by weight or less, 7.0% by weight or less, 6.5% by weight or less, 6.0% by weight or less, 5.5% by weight or less, 5.0% by weight or less, or 4.5% by weight or less.

[0050] In one embodiment of the present invention, 90% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, 99% by weight or more, 99.5% by weight or more (upper limit: 100% by weight) of the additives contained in the biomass masterbatch is made of a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof. In this embodiment, the unsaturated carboxylic acid and the polyolefin are maleic acid and polypropylene, respectively.

[0051] In one embodiment of the present invention, the additive may be a commercially available product, and specific examples thereof include RIKEAID MG-440P (manufactured by Riken Vitamin Co., Ltd.), MG-441P (manufactured by Riken Vitamin Co., Ltd.), MG-250P (manufactured by Riken Vitamin Co., Ltd.), POEM J-4081V (manufactured by Riken Vitamin Co., Ltd.), UMEX 1001 (manufactured by Sanyo Chemical Industries, Ltd.), UMEX 1010 (manufactured by Sanyo Chemical Industries, Ltd.), Chirabazole VR-01 (manufactured by Taiyo Kagaku Co., Ltd.), Chirabazole VR-07 (manufactured by Taiyo Kagaku Co., Ltd.), and Biosizer (manufactured by Riken Vitamin Co., Ltd.).

[0052] In one embodiment of the present invention, the additive may be biodegradable. By making the additive biodegradable, it is possible to prevent the additive from remaining in the natural world. In addition, when a non-biodegradable additive is used, there is a possibility that the biodegradation of the entire composition is inhibited, but when a biodegradable additive is used, there is an extremely low possibility that the biodegradation of the entire composition is inhibited. In addition, the substances listed in the Biodegradable Plastics Positive List (PL) (Classification No. B-3 (lubricants)) of the Japan Bioplastics Association (JBPA) are cited in their entirety by reference and incorporated herein, and serve as a lawful basis for amendment.

[0053] Here, biodegradation refers to the breaking of molecular bonds of a substance by enzymes produced by microorganisms in soil or water, and ultimately decomposing the substance into water and carbon dioxide. According to one embodiment, biodegradability means satisfying at least one of ISO 9408, ISO 9439, ISO 10707, JIS K 6950, JIS K 6951, JIS K 6953, or JIS K 6955.

[0054] In one embodiment of the present invention, the total content of rice, polypropylene and additives in the biomass masterbatch is 100% by weight.

[0055] In one embodiment of the present invention, there is also provided a biomass masterbatch raw material comprising rice and polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more. The description of the biomass masterbatch can also be applied to the biomass masterbatch raw material.

[0056] <Manufacturing method of biomass masterbatch> In one aspect of the present invention, there is provided a method for producing a biomass masterbatch, comprising kneading rice and polypropylene in a production apparatus, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more. In this way, by producing a biomass masterbatch by combining a specific rice with a specific polypropylene, the concentration of rice in the biomass masterbatch can be increased. In one embodiment of the present invention, the content ratio of rice in the biomass masterbatch can be set to be more than 50% by weight.

[0057] In one aspect of the present invention, there is provided a method for producing a biomass master batch, comprising kneading rice and polypropylene in a production apparatus, the polypropylene having an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, and a flexural modulus of 1000 MPa or less, the rice content in the biomass master batch being more than 50% by weight, and when 3 g of the biomass master batch is stretched into a flat shape by hot pressing to produce a sample, the number of rice agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less. Thus, according to the present invention, even if the rice content is as high as more than 50% by weight, a biomass master batch with few agglomerates can be obtained.

[0058] In one embodiment of the present invention, the production method includes adding at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid ester, polyglycerin fatty acid ester, polyalkylene glycol, and a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof.

[0059] The description of the biomass masterbatch herein may also be applied to the method of making the biomass masterbatch.

[0060] In one embodiment of the present invention, various manufacturing devices can be used without limitation for mixing materials for producing a biomass master batch. However, when the rice to be fed into the manufacturing device is in an air-dried state, it is preferable to feed water into the manufacturing device, and by doing so, the rice is mixed in a heated state in the presence of water, and the gelatinization of the rice is started in the device, and the resin and the rice become amorphous when mixed, making it easier to mix. Therefore, it is preferable that the device is one that can be used when water is fed. Therefore, in one embodiment of the present invention, the gelatinization of the rice is started in the manufacturing device. In one embodiment of the present invention, the amount of water to be fed is preferably 1 to 10 parts by weight, or 2 to 6 parts by weight, relative to 100 parts by weight of rice.

[0061] (manufacturing equipment) In one embodiment of the present invention, the production apparatus may be a twin-screw extruder 100. The twin-screw extruder 100 has a first storage section 10, an input section 20, a rotation section 30, a dehydration section 50, a first degassing section 60, a second degassing section 70, a discharge section 80, a cooling section 90, and a cutting section 110, as shown in Figs.

[0062] In the description of the twin-shaft kneading device 100, an orthogonal coordinate system is shown in the drawings. X is the direction in which the rotation axis of the rotating part 30 described later extends, and is defined as the longitudinal direction X. Y corresponds to the width direction of the first storage part 10 intersecting with the longitudinal direction X, and is defined as the width direction Y. Z is the direction intersecting with the longitudinal direction X and the width direction Y, and is defined as the height direction Z. Details will be described below.

[0063] (First storage section 10) The first storage section 10 stores rice, resin, a compatibilizer (material), and the like, together with water as necessary. The first accommodation space S1 is formed so as to be long and extend in the longitudinal direction X of the space in which the twin-screw kneading device 100 is installed.

[0064] The first storage section 10 is configured to form a first storage space S1 that stores a plurality of rotating members 31, 32, 33, 34, 35, 36, 37, 38, 39, 41, 42 that constitute the rotating section 30. The first storage space S1 formed by the first storage section 10 is configured to be continuous from directly below the input section 20 to a portion connected to the second degassing section 70. In this embodiment, the first storage space S1 is configured such that the inner circumferential portion of the cross section is shaped like two arcs joined together, as shown in FIG. 4, so that the rotating members of the rotating section 30 have two rotation axes. The first storage section 10 can be provided with a heating device (not shown) such as a heater for adjusting the temperature of the first storage space S1. The above-mentioned heaters can be arranged in multiple locations, for example, in the longitudinal direction X of the first storage space S1 of the first storage section 10 so that the temperature can be adjusted for each specific section of the rotating members described later in the longitudinal direction X.

[0065] (Insertion section) The input unit 20 includes a hopper (feeder) capable of inputting the above-mentioned materials and water into the first storage space S1 as shown in Fig. 1. The hopper of the input unit 20 is formed in a funnel shape.

[0066] (Rotating part) The rotating unit 30 is rotatably arranged in the first storage space S1. The rotating unit 30 is configured such that a plurality of rotating members 31-39, 41, 42 are arranged in a row along a rotation axis parallel to the longitudinal direction X. The rotating members 31-39, 41, 42 are arranged in a biaxial row along the width direction Y as shown in FIG. 5. In this specification, the rotating member 31 corresponds to the first screw, the rotating member 32 corresponds to the first paddle, the rotating member 33 corresponds to the second screw, the rotating member 34 corresponds to the second paddle, the rotating member 35 corresponds to the fourth screw, the rotating member 41 corresponds to the sixth screw, and the rotating member 42 corresponds to the seventh screw. Each rotating member will be described in detail below.

[0067] (Rotary member 31) The rotating member 31 is disposed directly below the hopper of the feeding section 20 in the first storage space S1 of the first storage section 10. The rotating member 31 is configured to form a screw. In this specification, the portion of the first storage space S1 where the rotating member 31 is disposed is referred to as a material feeding section where materials and water are fed.

[0068] (Rotary members 32, 33) 5, the rotating member 32 is provided adjacent to the rotating member 31 on the downstream side of the rotating member 31 in the first housing space S1. The rotating member 32 is configured such that plate-shaped members are arranged along the rotation axis. The rotating member 32 is disposed between the rotating member 31 and the rotating member 33.

[0069] The rotating member 33 is provided adjacent to the rotating member 32 on the downstream side of the rotating member 32 in the first storage space S1. The rotating member 33 is configured to form a screw similar to the rotating member 31. The rotating member 33 has a shallower spiral groove than the rotating member 31. The rotating member 33 is configured to have a larger difference between the outermost and innermost circumferences in the radial direction of the spiral than the rotating member 31. The rotating member 33 is configured to have the same size as the outermost circumference of the rotating member 31 and to have a smaller innermost circumference than the rotating member 31. The portion of the first storage space S1 where the rotating members 32 and 33 are arranged can be called a resin dissolving portion that dissolves the resin input from the input portion 20.

[0070] (Rotating member 34) The rotating member 34 is a plate-shaped member arranged along a rotation axis in the same manner as the rotating member 32. The rotating member 34 is arranged downstream of the rotating shaft from the rotating member 33 in the first storage space S1. In FIG. 5, the rotating member 34 is illustrated as having one type of plate-like member thickness, but it does not have to be one type. The rotating member 34 is configured to be thinner than the rotating member 32 to exert more shear stress to disperse the material and perform uniform stirring. The part of the first storage space S1 where the rotating member 34 is arranged can be called a kneading section that kneads the material input from the input section 20. A dehydration section 50 is connected near the boundary between the rotating member 33 and the rotating member 34 to discharge gas-liquid components such as water added to the above-mentioned material. Details will be described later.

[0071] (Rotating member 35) The rotating member 35 is provided adjacent to the rotating member 34 on the downstream side of the rotating member 34 in the first storage space S1. The rotating member 35 is configured to form a screw similar to the rotating member 33. The rotating member 35 is configured so that the depth of the spiral groove is equal to that of the rotating member 33. The rotating member 35 is connected to a first degassing section 60 that degasses the material kneaded in the first storage space S1. This will be described in detail later.

[0072] (Rotating members 36-39) The rotating members 36 and 37 are provided adjacent to the rotating member 35 on the downstream side of the rotating member 35 in the first housing space S1. The rotating members 36 and 37 are configured to have plate-like members arranged side by side, similar to the rotating member 32. The rotating members 36 and 37 are formed with a spiral with small undulations, and the spirals of the rotating members 36 and 37 are configured to rotate in different directions.

[0073] The rotating members 38 and 39 are provided adjacent to the rotating member 37 on the downstream side of the rotating member 37 in the first housing space S1. The rotating members 38 and 39 are configured to form a screw similar to the rotating member 33. The screws of the rotating members 38 and 39 are configured to have the same spiral groove depth as the rotating member 33. The rotating members 38 and 39 are configured so that the spiral rotation directions are reversed.

[0074] By reversing the spiral rotation direction of the rotating members 36, 38 and the rotating members 37, 39 in this way, the material sent from the rotating member 35 is temporarily pushed back to the upstream side of the rotation axis by the rotating members 37, 39 and then moves to the downstream side. As a result, the material remains in the rotating members 36-39 for a relatively long time, and compression is performed to improve the density of the material. The part of the first storage space S1 where the rotating members 36-39 are arranged can be called a compression section where the material is compressed.

[0075] (Rotary members 41, 42) The rotating member 41 is provided adjacent to the rotating member 39 on the downstream side of the rotating members 35, 39 in the first storage space S1. The rotating member 42 is provided adjacent to the rotating member 41 on the downstream side of the rotating member 41 in the first storage space S1. The rotating members 41, 42 are configured to form a screw like the rotating member 33, and the rotating member 42 is configured to have a shorter spiral pitch than the rotating member 41. The rotating members 41, 42 are connected to a second degassing section 70 that degasses the material stored in the first storage space S1.

[0076] Thus, the rotating members 31 to 39, 41, and 42 include rotating member 31 having a spiral shape and arranged directly below feeding section 20, and rotating member 33 arranged downstream of rotating member 31 on the rotation axis and having a shallower spiral groove than rotating member 31. By configuring in this manner, even if it is usually difficult for at least a portion of the material to be sent downstream by the screw in a twin-screw kneading device, a biomass masterbatch can be efficiently produced by kneading in such a way that at least a portion of the material is sent downstream by rotating member 31.

[0077] The rotating members 31-39, 41, and 42 are provided with a rotating member 35 that is provided downstream of the rotating member 34 in the first storage space S1. A first degassing section 60 is connected to the vicinity of the rotating member 35. The first degassing section 60 is provided with a screw 61 and a third storage section 62. The screw 61 rotates around a rotation axis that is parallel to a direction intersecting with the rotation axis of the rotating members 31-39, 41, and 42, and is configured to be paired. The third storage section 62 is provided with a third storage space S3 that accommodates the screw 61, is connected to the first storage section 10, and is connected to a pump or the like that can discharge the gas generated in the first storage space S1 by suction. By configuring in this way, it is possible to further discharge unnecessary moisture while leaving the solid components of the material in the first storage space S1, similar to the dehydration section 50.

[0078] The rotating members 31 to 39, 41, and 42 include a rotating member 41 provided downstream of the rotating member 35 in the first storage space S1, and a rotating member 42 provided adjacent to the rotating member 41. A second degassing section 70 is connected to the vicinity of the rotating member 41. The second degassing section 70 includes a screw 71 and a fourth storage section 72. The screw 71 rotates around a rotation axis parallel to a direction intersecting the rotation axis of the rotating member 41, and is configured to be paired. The fourth storage section 72 includes a fourth storage space S4 that accommodates the screw 71, is connected to the first storage section 10, and is connected to a pump that can discharge the gas generated in the first storage space S1 by suction. By configuring in this way, it is possible to further discharge unnecessary moisture while leaving the solid components of the material in the first storage space S1, similar to the first degassing section 60. Furthermore, by connecting the second deaeration section 70 near the rotating member 41, which has a relatively large spiral pitch, instead of the rotating member 42, unnecessary moisture can be easily discharged from the first housing space S1.

[0079] The ratio of the rotating members 32, 34 to the overall length of the rotating members 31-39, 41, 42 in the longitudinal direction X (ie, kneading block ratio) can be, for example, 18 to 32%, or 22 to 27%.

[0080] (Dehydration section 50) The dehydration section 50 is configured to discharge (dehydrate) gas-liquid components such as moisture kneaded in the first accommodating section 10. The dehydration section 50 is connected to the first accommodating section 10 in a direction intersecting the rotation axes of the rotating members 33, 34 near the boundary between the rotating members 33 and 34 as shown in Fig. 5. Near the boundary between the rotating members 33 and 34 in the first accommodating space S1, the internal pressure in the first accommodating space S1 during kneading can be configured to be saturated vapor pressure.

[0081] As shown in FIG. 5, the dehydration unit 50 includes a screw 51 (corresponding to a third screw), a second storage unit 52, and a drive unit 53. The screw 51 is configured to rotate in a direction intersecting with the rotating members 31 to 39, 41, and 42, and is configured to be paired. The drive unit 53 is configured to include a motor that rotates the screw 51. The second storage unit 52 is connected to the first storage unit 10 as shown in FIG. 5, and includes a housing or the like that is provided with a second storage space S2 that accommodates the screw 51. The second storage unit 52 discharges moisture from the second storage space S2. The second storage unit 52 is provided with an opening (not shown) that can discharge moisture. The opening can be provided in an upper portion of the second storage unit 52, or the like.

[0082] As described above, the rotating members 31 to 39, 41, 42 are disposed between the rotating members 31 and 33, and include the rotating member 32 having plate-like members arranged side by side on the rotation axis, and the plate-like rotating member 34 disposed downstream of the rotation axis from the rotating member 33. The dehydration unit 50 is connected to the vicinity of the rotating members 33 and 34. The dehydration unit 50 includes a screw 51 and a second storage unit 52. The screw 51 rotates around an axis of rotation that is parallel to the width direction Y that intersects with the rotation axis, and is configured to form a pair. The second storage unit 52 includes a second storage space S2 that accommodates the screw 51, and is connected to the first storage unit 10 and has an opening that can discharge moisture. By configuring in this manner, it is possible to remove unnecessary moisture and the like while leaving solid components contained in the material in the first housing space S1 of the first housing part 10.

[0083] (First degassing section 60) The first degassing section 60 is configured to be connected to the first storage section 10 in the vicinity of where the rotating member 35 is disposed. As shown in FIG. 5, the first degassing section 60 includes a screw 61 (corresponding to the fifth screw), a third storage section 62, and a driving section 63. The screw 61 is configured to rotate in a direction intersecting the rotation axis of the rotating members 31 to 39, 41, and 42, and to be paired. The driving section 63 is configured to include a motor or the like that rotates the screw 61, similar to the dehydration section 50. The third storage section 62 is connected to the first storage section 10 in the vicinity of the rotating member 35, and includes a housing or the like that has a third storage space S3 that accommodates the screw 61. The third storage section 62 is connected to a vacuum pump or the like that can suck gas and liquid components generated in the first storage space S1 via the third storage space S3.

[0084] (Second degassing section 70) The second degassing section 70 is configured to be connected to the first storage section 10 in the vicinity of where the rotating member 41 is disposed. As shown in FIG. 5, the second degassing section 70 includes a screw 71 (corresponding to an eighth screw), a fourth storage section 72, and a drive section 73. The screw 71 is configured to rotate in a direction intersecting the rotation axes of the rotating members 31-39, 41, and 42, and to form a pair. The drive section 73 is configured to include a motor and the like that rotates the screw 71, similar to the first degassing section 60. The fourth storage section 72 is connected to the first storage section 10 in the vicinity of the rotating member 41, and includes a housing and the like that is provided with a fourth storage space S4 that accommodates the screw 71. The screw 51 of the dehydration section 50, the screw 61 of the first degassing section 60, and the screw 71 of the second degassing section 70 extend in the width direction Y so as to approach the rotating members 31-39, 41, and 42 without interfering with the operation of the rotating members 31-39, 41, and 42. The fourth storage section 72 is connected to a vacuum pump or the like capable of sucking the gas-liquid components generated in the first storage space S1 through the fourth storage space S4. Note that the second storage section 52, the third storage section 62, and the fourth storage section 72 are illustrated in a simplified manner in FIG. 5 for convenience.

[0085] In this way, by configuring the twin-screw kneading apparatus 1 to have two degassing sections, the first degassing section 60 and the second degassing section 70, when kneading is performed using a material with a high moisture content, dehydration can be performed more efficiently by the first degassing section 60 and the second degassing section 70, and unnecessary moisture and the like can be removed from the biomass master batch.

[0086] (Discharge section 80) The discharge section 80 is provided adjacent to the outside of the downstream side of the first storage section 10 as shown in FIG. 1 and the like. The discharge section 80 is provided to form the degassed material (hereinafter also referred to as kneaded material) in the first storage space S1 of the first storage section 10 into a string shape. In this embodiment, the discharge section 80 is configured to include a member having a plurality of holes provided at an end of the first storage section 10 in the longitudinal direction X, which is a portion connecting the first storage space S1 of the first storage section 10 to the outside. The discharge section 80 can be heated by providing a heating device such as a heater, similar to the rotating members 31 to 39, 41, 42, etc. arranged in the first storage section 10.

[0087] (Cooling section 90) The cooling section 90 is provided to cool the string-like kneaded material discharged from the first storage section 10. The cooling section 90 includes a conveyor 91, a liquid supply section 92, and a gas supply section 93, as shown in FIG.

[0088] The conveyor 91 is provided adjacent to the discharge section 80. The conveyor 91 is configured to transport the kneaded material discharged from the discharge section 80 to the cutting section 110 as shown in FIG. In this embodiment, the conveyor 91 is configured to extend along an oblique direction inclined from the longitudinal direction X toward the positive direction of the height direction Z as shown in Fig. 2. However, the extension direction of the conveyor 91 is only an example, and the specific conveying direction of the conveyor is not limited to that shown in Fig. 2 etc. as long as the kneaded material can be conveyed to the cutting section 110.

[0089] The liquid supply unit 92 is configured to supply cooling water of a relatively low temperature to the kneaded material transported on the conveyor 91. The liquid supply unit 92 is configured by arranging a plurality of spray nozzles in the transport direction of the conveyor 91, the spray nozzles being connected to a cooling water supply source by a hose or the like.

[0090] The gas supplying unit 93 is configured to supply gas such as air adjusted to a predetermined temperature to the kneaded material transported on the conveyor 91. The gas supplying unit 93 is configured to include a duct (not shown) and a blower connected to the duct and capable of spraying gas toward the kneaded material on the conveyor 91.

[0091] (cutting section 110) The cutting section 110 is configured to cut the kneaded material discharged from the discharge section 80 and cooled in the cooling section 90 to a predetermined length. The cutting section 110 can include a feed roller 111 that feeds the kneaded material, and a cutting roller 112 equipped with a blade that cuts the fed kneaded material, as shown in Fig. 1. The cooled kneaded material can be subjected to a drying process in a facility such as a drying chamber (which can be called a drying section).

[0092] The average diameter of the biomass master batch pelletized through the cutting unit 110 is 0.5 to 30 mm, 0.5 to 20 mm, 0.5 to 10 mm, 1 to 8 mm, 2 to 6 mm, or 2 to 5 mm. The average diameter of the biomass master batch obtained in the examples was 4 to 5 mm. The method for measuring the average diameter of the biomass master batch can be the same as the method for measuring the average diameter of rice.

[0093] In one embodiment of the present invention, the temperature of the portion of the first storage space S1 corresponding to the input portion is, for example, 40 to 90°C, 50 to 85°C, or 70 to 82°C from the viewpoint of suppressing bumping of the moisture contained in the biomass material.

[0094] In one embodiment of the present invention, the temperature of the portion of the first housing space S1 that corresponds to the resin melting portion is, for example, 120 to 190°C, 130 to 170°C, 132 to 165°C, or 140 to 162°C from the viewpoint of melting the resin.

[0095] In one embodiment of the present invention, the temperature of the portion of the first housing space S1 corresponding to the kneading section is, for example, 130 to 195°C, 150 to 190°C, or 160 to 185°C from the viewpoint of efficient kneading.

[0096] In one embodiment of the present invention, the temperature of the portion of the first housing space S1 corresponding to the compression section is, for example, 125 to 193°C, 145 to 188°C, or 155 to 182°C from the viewpoint of efficient compression.

[0097] In one embodiment of the present invention, the connecting portion between the first degassing section 60 and the second degassing section 70 in the first accommodation space S1 has a temperature of 125 to 193°C, 145 to 188°C, or 155 to 182°C.

[0098] In one embodiment of the present invention, the temperature of the portion corresponding to the discharge portion is, for example, 125 to 193°C, 145 to 188°C, or 155 to 182°C from the viewpoint of efficient discharge.

[0099] In this way, the biomass masterbatch of one embodiment of the present invention can be obtained. The biomass masterbatch is used for at least one application selected from the group consisting of eating utensils, food containers, packaging materials, agricultural materials, electronic device housings, home appliance housings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily necessities. Among them, it is preferable to apply it to eating utensils such as tray containers and cutlery. More preferably, it is preferable to apply a molded product obtained by molding a resin mixture containing the masterbatch and a diluting resin to the above application.

[0100] The resin mixture and its manufacturing method, as well as the molded article and its manufacturing method, will be described below.

[0101] <Resin mixture and method for producing same> In one aspect of the present invention, there is provided a resin mixture containing a biomass masterbatch and a diluent resin, the resin mixture having a rice content of more than 50% by weight. In another aspect of the present invention, there is provided a method for producing the resin mixture, the method comprising mixing the biomass masterbatch and the diluent resin.

[0102] In one embodiment of the present invention, the biomass masterbatch and the diluent resin can be mixed by appropriately applying a known technique. For example, the biomass masterbatch and the diluent resin can be mixed by using a known mixing device such as a tumbler mixer, a ribbon blender, or a V-type mixer.

[0103] In one embodiment of the present invention, the content ratio of the biomass masterbatch in the resin mixture is 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, or 70% by weight or more. In one embodiment of the present invention, the content ratio of the biomass masterbatch in the resin mixture is 90% by weight or less, 85% by weight or less, 80% by weight or less, or 75% by weight or less.

[0104] In one embodiment of the invention, the content of the diluent resin in the resin mixture is 10% by weight or more, 15% by weight or more, 20% by weight or more, or 25% by weight or more. In one embodiment of the invention, the content of the diluent resin in the resin mixture is 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, or 30% by weight or less.

[0105] In one embodiment of the present invention, the rice content in the resin mixture may be 10% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, or more than 50% by weight. In particular, when the rice content is 25% by weight or more, the biomass material is a carbon-neutral material and serves as a measure against global warming. In one embodiment of the present invention, the rice content in the resin mixture is 90% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, or 60% by weight or less.

[0106] In one embodiment of the present invention, the total content of the biomass masterbatch and the diluent resin is 100% by weight in the resin mixture.

[0107] In one embodiment of the present invention, the diluent resin is preferably a polyolefin such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), or polybutene, or an ethylene-based copolymer such as ethylene-vinyl acetate copolymer (EVA) or ethylene-ethyl acrylate copolymer (EEA). It is appropriate.

[0108] The commercially available diluent resin is not particularly limited, but Novatec (registered trademark) MA3, MA1B, BC2E, and BC03B manufactured by Japan Polypropylene Corporation, or Prime Polypropylene J106G and J107G manufactured by Prime Polymer Co., Ltd. are suitable.

[0109] <Molded products and their manufacturing methods> In one embodiment of the present invention, a molded article is provided which is obtained by molding the resin mixture.

[0110] In one embodiment of the present invention, the molding process is inflation molding, sheet molding, or injection molding, and is preferably injection molding.

[0111] In one embodiment of the present invention, the molded product is a tray, a container, a cutlery or other eating utensil.

[0112] In one embodiment of the present invention, the molded product is a film or a sheet. When the molded product is a film, the thickness is preferably 10 μm to 100 μm, and when the molded product is a sheet, the thickness is preferably more than 100 μm and 1 mm or less. The thickness of the molded product can be measured according to JIS B7503:2017.

[0113] In one embodiment of the present invention, the molded product is used for at least one application selected from the group consisting of eating utensils, food containers, packaging materials, agricultural materials, electronic device housings, home appliance housings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily necessities. Among them, by obtaining containers such as trays and eating utensils such as cutlery as molded products, the molded products have an excellent balance of tensile strength (stress, elastic modulus, and elongation), excellent Charpy impact strength, and suppressed coloring.

[0114] The temperature at which the resin mixture is molded is preferably 120 to 190°C, and more preferably 140 to 180°C, from the viewpoint of achieving both suppression of discoloration and strength of the resulting molded product.

[0115] The present application encompasses the following aspects and configurations.

[0116] 1. A biomass master batch produced by kneading rice and polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more.

[0117] 2. A biomass masterbatch comprising rice and polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and a rice content of more than 50% by weight, and when 3 g of the biomass masterbatch is stretched into a flat shape using a hot press molding machine (170°C, 15 MPa pressure) in combination with a 0.3 mm thick stainless steel thickness gauge to prepare a sample, the number of starch agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less.

[0118] 3. The biomass masterbatch according to 1, wherein the rice content is greater than 50% by weight.

[0119] 4. The biomass masterbatch according to any one of 1. to 3., which contains at least one additive selected from the group consisting of glycerol, polyglycerol, glycerol fatty acid esters, polyglycerol fatty acid esters, polyalkylene glycol, and polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof.

[0120] 5. A method for producing a biomass masterbatch, comprising kneading rice and polypropylene in a production apparatus, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, a flexural modulus of 1000 MPa or less, and an elongation rate of the rice of 95% or more.

[0121] 6. A method for producing a biomass masterbatch, comprising kneading rice and polypropylene in a production apparatus, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, and a flexural modulus of 1000 MPa or less, wherein the rice content in the biomass masterbatch is more than 50% by weight, and when 3 g of the biomass masterbatch is stretched into a flat shape by thermocompression molding to produce a sample, the number of rice agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less.

[0122] 7. The manufacturing method according to 5., wherein the rice content in the biomass masterbatch is greater than 50% by weight.

[0123] 8. The production method according to any one of 5. to 7., comprising a step of adding at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid esters, polyglycerin fatty acid esters, polyalkylene glycols, and polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof.

[0124] 9. A manufacturing method described in any one of 5. to 8., wherein the gelatinization of the rice is initiated within the manufacturing equipment.

[0125] 10. A resin mixture comprising the biomass masterbatch according to any one of 1. to 9. and a dilution resin, the resin mixture having a rice content of more than 50% by weight.

[0126] A molded article obtained by molding the resin mixture described in 11.10.

[0127] 12. The molded article according to claim 11, wherein the molding process is injection molding.

[0128] 13. The molded product according to 11 or 12, which is used for at least one application selected from the group consisting of eating utensils, food containers, packaging materials, agricultural materials, housings for electronic devices, housings for home appliances, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily miscellaneous goods. EXAMPLES

[0129] The present invention will be described in more detail below with reference to examples, although the technical scope of the present invention is not limited to the following examples.

[0130] <Preparation of biomass master batch> Example 1 (Material preparation) As materials, As rice, 78.7 parts by weight (rice solids) of polished rice A (moisture content 11% by weight) having the elongation rate shown in Table 1 was used. Weight: 70 parts by weight), Resin A is 26 parts by weight of polypropylene as shown in Table 2, and As an additive, 4 parts by weight of maleic anhydride modified polypropylene (MG-441P manufactured by Riken Vitamin Co., Ltd.) was used.

[0131] The elongation rate of polished rice A was calculated as follows.

[0132] 1. Three test tubes (PYREX, φ18mm x 150mm) were prepared (n=3) containing 4.0g of polished rice A (rounded off to the nearest tenth) in 20.0g of ion-exchanged water (25℃). The rice was adjusted so that the height of the rice was as horizontal as possible in the water, and the height of the rice was measured at its highest point (=Xcm).

[0133] 2. The three test tubes prepared above were placed in a thermostatic chamber with an internal temperature of 67°C and heated for three hours.

[0134] 3. Each test tube was removed from the thermostatic chamber and the height of the rice was measured at its highest point (=Y cm).

[0135] 4. The elongation rate (=(YX) / X×100) for each tester was measured, and the arithmetic mean value of n=3 was calculated to determine the elongation rate of polished rice A (rounded off to the nearest tenth). The elongation rates of the other polished rice were also measured in the same manner.

[0136] In addition, the MFR (230℃ / 2.16kgf) of the resin (polypropylene) is JIS K The measurements were performed in accordance with 7210-1:2014 (ISO1133-1:2011), Plastics - Determination of melt flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics - Part 1: Standard test method.

[0137] The melting point of the resin (polypropylene) was measured using a constant test force extrusion type capillary tube rheometer flow tester (CFT-500EX) manufactured by Shimadzu Corporation.

[0138] The flexural modulus of the resin (polypropylene) was measured in accordance with JIS K7171:2016 (Plastics - Determination of flexural properties).

[0139] (Mixing conditions) The above materials were kneaded using a twin-screw kneader 100 rotating in the same direction as shown in FIG. 1 etc., and cut by a cutting section 110 to produce the biomass master batch of Example 1.

[0140] The L / D ratio of the rotating members of the twin-screw kneading apparatus 100 ((total length of the screws in the x direction)÷(cross-sectional diameter of one screw) in FIG. 5) was set to 50.

[0141] The above-mentioned rotating members 31 to 39, 41, and 42 were used as the rotating members of the rotating section 30. The ratio of the rotating members 32, 34 to the overall length of the rotating members 31 to 39, 41, and 42 in the longitudinal direction X (kneading block ratio) was 25%.

[0142] The above-mentioned materials were supplied to the first storage space S1 from the input section 20. If the material was solid, it was supplied from the hopper, and if the material was liquid, it was supplied from the hopper using a tube pump. In addition, 3 parts by weight (i.e., 2.1 parts by weight in Example 1) of distilled water per 100 parts by weight of rice was also supplied to the first storage space S1 from the hopper using a tube pump.

[0143] The rotation speed of the rotating members 31 to 39, 41, and 42 was set to 280 rpm. The portion of the first storage space S1 corresponding to the input section was heated to 80°C, the portion corresponding to the resin dissolving section to 160°C, and the portion corresponding to the kneading section to 180°C. When the material was sent from the rotating member 33 to the rotating member 34, water was removed by the dehydration section 50. The connecting section of the first deaeration section 60 and the second deaeration section 70 in the first storage space S1 was heated to 160°C, the portion corresponding to the compression section to 170°C, and the discharge section 80 to 180°C.

[0144] [Examples 2 and 3 and Comparative Examples 1 to 7] Biomass masterbatches of Examples 2 and 3 and Comparative Examples 1 to 7 were produced in the same manner as in Example 1, except that the materials and their contents were changed to those shown in Table 3.

[0145] <Result> (aggregation level, coloring) Of the biomass master batch obtained by being sent from the cutting section 110, 3 g was taken out and stretched into a flat shape by thermocompression molding using a hot press at 170° C. to prepare a sample.

[0146] Rice agglomeration was confirmed by observing rice agglomerates (diameter 0.1 mm or more) under a microscope. Evaluation was performed according to the following criteria. Three samples were prepared, and the total number of agglomerates in the three samples was divided by 3 and rounded off to the nearest tenth.

[0147] [Evaluation criteria for rice agglomerates] A: No agglomerates were observed in the sample.

[0148] B: Fewer than 10 agglomerates were found in the sample.

[0149] C: 11 to 20 aggregates can be identified in the sample.

[0150] D: 21 or more aggregates were found in the sample.

[0151] ×: Burnt spots were observed in the sample.

[0152] The coloring property was evaluated by visually observing the sample and was rated according to the following criteria.

[0153] [Coloring standards] ○: Not browned, ×: Colored brown.

[0154] (MFR of biomass masterbatch) The MFR (190°C / 10 kgf) of the biomass master batch was measured in the same manner as in the measurement of the MFR (190°C / 2.16 kgf), except that the weight (load) of the weight was changed to 10 kgf.

[0155] (Kneading torque) The kneading torque is the load rate relative to the torque limit of 100% of the screw drive motor in the twin-screw kneader, and is displayed on the control panel screen.

[0156] (Strength (Stress)) The strength (stress) is a value obtained in accordance with JIS K7162-2:1994 Plastics - Test methods for tensile properties, Part 2.

[0157] (Elasticity Modulus) The elastic modulus is a value obtained in accordance with JIS K7162-2:1994 Plastics - Test methods for tensile properties, Part 2.

[0158] (stretch) The elongation is a value obtained in accordance with JIS K7162-2:1994 Plastics - Test method for tensile properties, Part 2. The tensile speed is 100 mm / min.

[0159] (Sharpy) Charpy values ​​are obtained in accordance with JIS K7111-1:2012-Part 1: Non-instrumented impact test.

[0160] (Evaluation of injection moldability) A resin mixture with a rice content of 51% by weight was obtained by uniformly mixing 73 parts by weight of the biomass master batch obtained in each Example and Comparative Example with 27 parts by weight of Novatec MA3 (Japan Polypropylene Corporation) as a dilution resin using a tumbler mixer. The resin mixture was molded using two methods, pin gate and direct gate, using an injection molding machine.

[0161] Formability evaluation criteria ○: No clogging occurs inside the injection molding machine, and molded products can be produced according to the dimensions.

[0162] △: Although some clogging occurs inside the injection molding machine, it is possible to mold parts according to the dimensions.

[0163] ×△: Clogging occurs frequently inside the injection molding machine, but some of the machines are able to mold products according to the dimensions.

[0164] ×: Clogging occurred inside the injection molding machine, and it was not possible to mold a molded product according to the dimensions.

[0165] [Table 1]

[0166] [Table 2]

[0167] [Table 3]

[0168] The masterbatches of Examples 1 to 3 have an excellent balance of tensile strength (stress, elastic modulus, and elongation), excellent Charpy impact strength, and suppressed coloring. The moldability is excellent when mixed to produce a molded product. The injection moldability (pin gate) of Example 2 was rated △ because the aggregation level was B (i.e., the number of aggregates was slightly large) and the size of the aggregated particles was slightly large, making clogging likely to occur.

[0169] In Comparative Example 1, when the master batch and dilution resin were mixed to mold a pin-gate molded product, clogging occurred in the injection molding machine and the molded product could not be molded according to the dimensions. This is thought to be due to the fact that the resin and rice were not mixed uniformly and the rice was phase-separated.

[0170] In Comparative Example 2, when the master batch was mixed with dilution resin to mold a pin-gate molded product, clogging occurred in the injection molding machine and it was not possible to mold a molded product according to the dimensions. This is thought to be because the MFR of the polypropylene was low, which resulted in a low MFR for the obtained master batch, and clogging occurred due to this low MFR.

[0171] In Comparative Example 3, polypropylene with a high melting point and flexural modulus was used, so the kneading torque was high and there were many rice aggregates. In Comparative Example 3, biomass master batch pellets were obtained and the MFR value was measured, but the value is thought to be a direct reflection of the characteristics derived from the resin that was phase-separated from the rice.

[0172] In Comparative Example 4, the polypropylene did not flow as expected, the kneading torque was high, and the biomass masterbatch could not be obtained in the form of pellets. The rice in the biomass masterbatch was completely burnt, so that no moldability evaluation was performed.

[0173] In Comparative Example 5, the resin and rice were not mixed uniformly, and the rice was phase-separated, resulting in an agglomeration level of C. Unlike Comparative Example 1, although some clogging occurred, a molded product could be produced according to the dimensions because the size of the agglomerated grains was small.

[0174] In Comparative Example 6, the resin and rice were not mixed uniformly, and the rice was phase-separated, resulting in an aggregation level of B, and the size of the aggregated particles was also large. When the resin was mixed with dilution resin to mold a pin-gate molded product, clogging occurred in the injection molding machine, and the molded product could not be molded according to the dimensions.

[0175] The master batch of Comparative Example 7, like Comparative Example 2, had low MFR (thermal fluidity), and some defects occurred during injection molding even with a direct gate.

Claims

1. A biomass masterbatch produced by kneading rice and polypropylene, The polypropylene has an MFR (230° C. / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150° C. or less, and a flexural modulus of 1000 MPa or less, The biomass masterbatch, wherein the elongation rate of the rice is 95% or more.

2. A biomass master batch comprising rice and polypropylene, wherein the polypropylene has an MFR (230°C / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150°C or less, and a flexural modulus of 1000 MPa or less, and the rice content is more than 50% by weight, and when 3 g of the biomass master batch is stretched into a flat shape using a hot press molding machine (170°C, 15 MPa pressure) in combination with a 0.3 mm thick stainless steel thickness gauge to prepare a sample, the number of agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less.

3. 2. The biomass masterbatch of claim 1, wherein the rice content is greater than 50% by weight.

4. The biomass masterbatch according to claim 1 or 2, comprising at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid esters, polyglycerin fatty acid esters, polyalkylene glycols, and polyolefin resins modified with unsaturated carboxylic acids or derivatives thereof.

5. The method includes kneading rice and polypropylene in a manufacturing apparatus, The polypropylene has an MFR (230° C. / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150° C. or less, and a flexural modulus of 1000 MPa or less, A method for producing a biomass masterbatch, wherein the elongation rate of rice is 95% or more.

6. The method includes kneading rice and polypropylene in a manufacturing apparatus, the polypropylene has an MFR (230° C. / 2.16 kgf) of 10 g / 10 min or more, a melting point of 150° C. or less, and a flexural modulus of 1000 MPa or less; the content of said rice in said biomass master batch is more than 50% by weight, and when 3 g of said biomass master batch is stretched into a flat shape by hot pressing to produce a sample, the number of agglomerates having a diameter of 0.1 mm or more observed in the sample is 10 or less.

7. The method according to claim 5, wherein the content of the rice in the biomass masterbatch is greater than 50% by weight.

8. The method according to claim 5 or 6, further comprising the step of adding at least one additive selected from the group consisting of glycerol, polyglycerol, glycerin fatty acid ester, polyglycerin fatty acid ester, polyalkylene glycol, and a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof.

9. The method according to claim 5 or 6, wherein the gelatinization of the rice is initiated within the production equipment.

10. A rice-containing biomass masterbatch comprising the biomass masterbatch according to claim 1 or 2 and a diluting resin. The resin mixture has a content of more than 50% by weight.

11. A molded article obtained by molding the resin mixture according to claim 10.

12. The molded article according to claim 11, wherein the molding process is injection molding.

13. The molded product according to claim 11, which is used for at least one application selected from the group consisting of eating utensils, food containers, packaging materials, agricultural materials, electronic device housings, home appliance housings, building material parts, automobile parts, motorcycle parts, aircraft parts, railway vehicle parts, and daily necessities.

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